Just seeing off the BOth anniversary of the Institute of Chemistry, Chinese Academy of Sciences （ICCAS）, we are here with pleasure to conduct A Special Column for Young Scientists at ICCAS published in Chinese Chemi...Just seeing off the BOth anniversary of the Institute of Chemistry, Chinese Academy of Sciences （ICCAS）, we are here with pleasure to conduct A Special Column for Young Scientists at ICCAS published in Chinese Chemistry Letters （CCL） endeavoring to disseminate positive energy of several enthusiastic chemists and spread their recent research to the global scientific community.展开更多
The structure and electronic properties of Co_(2)Ge_(10)^(-)anion and its neutral counterpart were investigated by anion photoelectron spectroscopy and theoretical calculations.The experimental vertical detachment ene...The structure and electronic properties of Co_(2)Ge_(10)^(-)anion and its neutral counterpart were investigated by anion photoelectron spectroscopy and theoretical calculations.The experimental vertical detachment energy of Co_(2)Ge_(10)^(-)was measured to be 2.86±0.08 eV.The lowest-energy isomer of Co_(2)Ge_(10)^(-)is in a doublet state and has a cage-like structure with Cs symmetry,which can be constructed by a tetragonal bipyramid on top of a pentagonal bipyramid and these two bipyramid structures share a common Co atom.The most stable structure of neutral Co_(2)Ge_(10)resembles its anionic counterpart and it is in a triplet state.The natural population analysis showed that the inner Co atom of both the anionic and neutral Co_(2)Ge_(10)acquires negative charge from the neighboring Ge atoms.The outer Co atom has a larger spin moment than the inner Co atom,indicating that the magnetic moments of Co_(2)Ge_(10)^(-/0)are mainly contributed by the outer Co atom.Analyses of the density of states and molecular orbitals indicated that there are a few highly delocalized molecular orbitals in Co_(2)Ge_(10)^(-),which are mainly contributed by Ge 4s atomic orbitals.展开更多
Institute of Chemistry,Chinese Academy of Sciences(ICCAS)was established in 1956.ICCAS is a multidisciplinary research institute dedicated to the basic research in broad fields of chemical sciences,and to the key deve...Institute of Chemistry,Chinese Academy of Sciences(ICCAS)was established in 1956.ICCAS is a multidisciplinary research institute dedicated to the basic research in broad fields of chemical sciences,and to the key development of the innovative high-technology aiming at the imperative national needs and important strategic targets,as well as to the collaborative high-technology applications and transfers.With the development of 60 years,ICCAS has become one of the leading chemistry institutions in China with high international visibility.展开更多
Nucleation,which is the initial step of crystallization,critically governs the polymer crystallization behavior,influencing the crystallization temperature,kinetics,and morphology.However,the direct observation of the...Nucleation,which is the initial step of crystallization,critically governs the polymer crystallization behavior,influencing the crystallization temperature,kinetics,and morphology.However,the direct observation of the nucleation process in polymers remains elusive owing to spatial and temporal resolution limitations.This feature article summarizes the recent progress in understanding polymer nucleation within confined and interface-dominated environments,focusing on three representative systems:anodic aluminum oxide templates and nanocomposites containing nanoparticles or nanosheets.The interplay between finite size and interfacial effects has revealed some novel phenomena,such as homogeneous nucleation,surface nucleation,prefreezing,and supernucleation.展开更多
It was in the 1980s that research on somatostatin(SST)in Alzheimer’s disease(AD)truly gained traction,demonstrating consistent colocalization with amyloid-β(Aβ),along with massive SST/SST cell losses(Almeida,2024)....It was in the 1980s that research on somatostatin(SST)in Alzheimer’s disease(AD)truly gained traction,demonstrating consistent colocalization with amyloid-β(Aβ),along with massive SST/SST cell losses(Almeida,2024).Although the field already had some grasp over the neuroendocrine and hypothalamic functions of the peptide,very little was known about the GABAergic interneurons(SST-INs)that synthesize it in cortical/hippocampal regions.Quite excitingly,over 40 years later,research has grown effervescent.展开更多
Picralima nitida Durand and Hook,(fam.Apocynaceae)is a West African plant with varied applications in African folk medicine.Various parts of the plant have been employed ethnomedicinally as remedy for fever,hypertensi...Picralima nitida Durand and Hook,(fam.Apocynaceae)is a West African plant with varied applications in African folk medicine.Various parts of the plant have been employed ethnomedicinally as remedy for fever,hypertension,jaundice,dysmenorrheal,gastrointestinal disorders and malaria.In order to reveal its full pharmacological and therapeutic potentials,die present review focuses on the current medicinal uses,phytochemistry,pharmacological and toxicological activities of this species.Literature survey on scientific journals,books as well as electronic sources have shown the isolation of alkaloids,tannins,polyphenols and steroids from different parts of the plant,pharmacological studies revealed that the extract or isolated compounds from this species posses analgesic,anti-inflammatory,hypoglyceamic,hypotensive,antiplasmodial,antimicrobial,antiulcer and antitumorigenic activities.Results from various scientific investigations to date have revealed the potential of the extract from the plant or isolated compounds for use in the treatment and prevention of various kinds of human diseases.However,further studies on the extracts and pure compounds from this species is required to completely assess its phytoc-hemical,pharmacological and toxicological profile as well as the mechanism of action behind these pharmacological activities exhibited by the compounds isolated from this species.展开更多
The electrochemistry of polyaniline synthesized electrochemically in acidic solution under light irradiation has been studied as a function of the applied potentials, the concentration and acidity of electrolyte as we...The electrochemistry of polyaniline synthesized electrochemically in acidic solution under light irradiation has been studied as a function of the applied potentials, the concentration and acidity of electrolyte as well as pH at applied potentials in the rang+0.40 to-0.5V vs. SCE. It is concluded that under selected experimental conditions the reduced repeat groups in polyaniline are oxidized by air in the dark and that this oxidation process can be strongly photocatalyzed.展开更多
Organic photovoltaics and field-effect transistors have attracted considerable attention due to the easy fabrication,low cost,light weight,and flexibility.Unsymmetrical conjugated building blocks are widely utilized f...Organic photovoltaics and field-effect transistors have attracted considerable attention due to the easy fabrication,low cost,light weight,and flexibility.Unsymmetrical conjugated building blocks are widely utilized for the design of new organic π-functional materials in order to achieve high-performance electronic devices,which has become a hot research topic in recent years.In this review,we summarized some typical organic π-functional materials with regioregular conjugated backbones with unsymmetrical electron-deficiency moieties and focused on the influence of regiochemistry on the final device performance.展开更多
Diphenylchlorin (DPC) and diphenylbacteriochlorin (DPBC) were synthesized for the first time from reduction of 5,10-diphenylporphyrin (DPP). As photosensitizers they have sizable absorption in the red region of the vi...Diphenylchlorin (DPC) and diphenylbacteriochlorin (DPBC) were synthesized for the first time from reduction of 5,10-diphenylporphyrin (DPP). As photosensitizers they have sizable absorption in the red region of the visible spectrum. The high yield of DPC.-photosensitized generation Of O-1(2), and the EPR studies in homogenerous solution showed that the photodynamic action of DPP-based photosensitizers may proceed via type I and type II machanisms.展开更多
Dendrite growth of lithium(Li)metal anode severely hinders its practical application,while the situation becomes more serious at low temperatures due to the sluggish kinetics of Liion diffusion.This perspective is int...Dendrite growth of lithium(Li)metal anode severely hinders its practical application,while the situation becomes more serious at low temperatures due to the sluggish kinetics of Liion diffusion.This perspective is intended to clearly understand the energy chemistry of lowtemperature Li metal batteries(LMBs).The lowtemperature chemistries between LMBs and traditional Liion batteries are firstly compared to figure out the features of the lowtemperature LMBs.Li deposition behaviors at low temperatures are then discussed concerning the variation in Liion diffusion behaviors and solid electrolyte interphase(SEI)features.Subsequently,the strategies to enhance the diffusion kinetics of Li ions and suppress dendrite growth including designing electrolytes and electrode/electrolyte interfaces are analyzed.Finally,conclusions and outlooks are drawn to shed lights on the future design of highperformance lowtemperature LMBs.展开更多
The multi-bond dissociation dynamics of oxalyl bromide （（BrCO）2） has been investigated by DFT and CIS calculations. Upon the results, conclusion could be drawn that dissociation of C-Br bond of oxalyl bromide at t...The multi-bond dissociation dynamics of oxalyl bromide （（BrCO）2） has been investigated by DFT and CIS calculations. Upon the results, conclusion could be drawn that dissociation of C-Br bond of oxalyl bromide at the ground state （So） is of barfierless. After the absorption of a photon, （BrCO）2 is excited to the first excited state and one of its C-Br bonds is broken to yield Br ·＊ and BrCOCO· ＊ free radicals. In addition, BrCOCO · ＊ with high energy is apt to release energy, and ultimately, turns into BrCOCO ·of the ground state. The energy is adequate for BrCOCO· to break down into Br · and 2CO; at the same time the C-C and C-Br bonds of BrCOCO · free radicals dissociate.展开更多
A solid-phase synthesis of 1α-hydroxylation of 5,6-trans-vitamin D3 8 is described.The solid phase resin acts as a special protecting group, which gives a higher stereoselectivity in oxidation step than classical pro...A solid-phase synthesis of 1α-hydroxylation of 5,6-trans-vitamin D3 8 is described.The solid phase resin acts as a special protecting group, which gives a higher stereoselectivity in oxidation step than classical protecting groups. The stereochemistry control is favored by using high crosslinkage polymer support in a poor solvent. This work may be of benefit to the synthesis of vitamin D system.展开更多
For the first time,the mechanism of metal aluminum dissolution in NaF-ScF_(3) eutectic melts and the chemical interaction between the constituents of this mixture have been thoroughly studied by a combination of diffe...For the first time,the mechanism of metal aluminum dissolution in NaF-ScF_(3) eutectic melts and the chemical interaction between the constituents of this mixture have been thoroughly studied by a combination of differential thermal analysis(DTA),high temperature and solid-state nuclear magnetic resonance(NMR),and X-ray diffraction(XRD) coupled with the molecular dynamic simulations.The formation of an insoluble Al_(3)Sc alloy in molten(NaF-ScF_(3))_(eut)system was proven,and the chemical mechanism of this aluminothermic Al_(3)Sc alloy production was elucidated.Corresponding ex situ examinations bring to light the formation of NaScF_4 and solid solution of Na_(3)(Al,Sc)F_(6) in cooled bath.The molecular dynamics calculations of the bath allow us to construct the structural model and to predict viscosity,density and electrical conductivity of the reagent melt to help to optimize the conditions of the alloy synthesis.展开更多
A new method of synthesis of 2-(1,2-diferrocenylvinyl)benz- and azabenzimidazoles (3a-f), (4a-f) and 1’H,3’H(Me)-spiro-[(aza)benzimidazoline-2’,3-(1,2-diferrocenylcyclopropenes)] (5a-f) via reactions of diferroceny...A new method of synthesis of 2-(1,2-diferrocenylvinyl)benz- and azabenzimidazoles (3a-f), (4a-f) and 1’H,3’H(Me)-spiro-[(aza)benzimidazoline-2’,3-(1,2-diferrocenylcyclopropenes)] (5a-f) via reactions of diferrocenyl(methylsulfanyl)cyclopropenylium iodide (1) with aromatic o-diamines (2a-f) in the presence of Et3N (80°C - 82°C) is described. The structures of the resultant compounds are established using IR, 1H and 13C NMR spectroscopy, mass spectrometry and elemental analysis. The structure of one compound, cis-2-(1,2-diferrocenylvinyl)-1-methylbenzimidazole (3b), is confirmed by X-ray diffraction analysis. The electrochemical properties of compounds 3a, 3b, 3d and 5f are investigated using cyclic square wave voltammetry. Two electrochemical processes (I-II), attributed to oxidation of the ferrocene moieties, and the values of E0’(I), E0’(II), DE0’(II-I) and comporportionation constant Kcom are reported. The bioactivities of seven compounds 3a, 3c-f, 5d, 5f are evaluated. Compound 5f is the most active compound with a modest cytotoxic activity against six human cancer cell lines: U-251 (glioma), PC-3 (prostate cancer), K-562 (leukemia), HCT-15 (colon cancer), MCF-7 (breast cancer) and SKLU-1 (lung cancer).展开更多
As one of the fundamental and key disciplines of natural sciences, chemistry deals with the properties, composition, structure, transformation and applications of substances.It could be further divided into several br...As one of the fundamental and key disciplines of natural sciences, chemistry deals with the properties, composition, structure, transformation and applications of substances.It could be further divided into several branches, such as inorganic chemistry, organic chemistry, physical chemistry, polymer chemistry, analytical chemistry and chemical engineering.In recent years, many new branches and fields have emerged amide the continuous development of chemistry and its interdisciplinary research with mathematics, physics, astronomy, earth science, biology, medical science, materials science, and environmental science.展开更多
Flexible wearable optoelectronic devices fabricated fromorganic–inorganic hybrid perovskites significantly accelerate the developmentof portable energy,biomedicine,and sensing fields,but their poor thermal stabilityh...Flexible wearable optoelectronic devices fabricated fromorganic–inorganic hybrid perovskites significantly accelerate the developmentof portable energy,biomedicine,and sensing fields,but their poor thermal stabilityhinders further applications.Conversely,all-inorganic perovskites possessexcellent thermal stability,but black-phase all-inorganic perovskite filmusually requires high-temperature annealing steps,which increases energy consumptionand is not conducive to the fabrication of flexible wearable devices.In this work,an unprecedented low-temperature fabrication of stable blackphaseCsPbI3perovskite films is demonstrated by the in situ hydrolysis reactionof diphenylphosphinic chloride additive.The released diphenyl phosphateand chloride ions during the hydrolysis reaction significantly lower the phasetransition temperature and effectively passivate the defects in the perovskitefilms,yielding high-performance photodetectors with a responsivity of 42.1 AW−1 and a detectivity of 1.3×10^(14)Jones.Furthermore,high-fidelity imageand photoplethysmography sensors are demonstrated based on the fabricated flexible wearable photodetectors.This work provides a newperspective for the low-temperature fabrication of large-area all-inorganic perovskite flexible optoelectronic devices.展开更多
Polybutene-1(PB-1) is a semi-crystalline polymer with excellent mechanical properties. However, its practical application is significantly hindered by the slow Form Ⅱ-Ⅰ transition, which can take up to several days ...Polybutene-1(PB-1) is a semi-crystalline polymer with excellent mechanical properties. However, its practical application is significantly hindered by the slow Form Ⅱ-Ⅰ transition, which can take up to several days to complete. While prior research established that long-chain branching(LCB) structures synthesized via ω-alkenylmethyldichlorosilane copolymerization-hydrolysis(ACH) chemistry markedly accelerate this transition, this work demonstrates that H-shaped LCB structures constructed through copolymerization with 1,9-decadiene exhibit the capability to facilitate Form Ⅱ-Ⅰ transition in most systems evaluated herein. However, low branching efficiency concurrently generates extended alkyl pendant chains, which impose pronounced steric-hindrance-driven suppression on the transition kinetics, thereby substantially diminishing the net acceleration effect of the LCB structures, even resulting in a net retardation effect in certain systems. Notably, a significant synergistic acceleration effect emerged between the H-shaped LCB structures and propylene comonomer units. These findings confirm that the H-shaped LCB structures play a role in promoting the Form II-I transformation process, which is independent of the synthetic pathways, thereby providing more strategies for addressing the long-standing processing problems of PB-1.展开更多
This article discusses potential solutions to overcome current limitations for clinical implementation of Mg implants by forming the biocompatible hybrid PEO-based inhibitor-and polymer-containing coatings for a contr...This article discusses potential solutions to overcome current limitations for clinical implementation of Mg implants by forming the biocompatible hybrid PEO-based inhibitor-and polymer-containing coatings for a controlled corrosion degradation of the bioresorbable material.Multifunctional hybrid coatings were obtained on MA8 magnesium alloy.The porous ceramic-like coating synthesized by plasma electrolytic oxidation served as a base for further modification with bioresorbable polymer(polycaprolactone,PCL)contained halloysite nanotubes(HNTs)with corrosion inhibitor(benzotriazole,BTA).The method for HNT impregnating with BTA and introducing them into the matrix of PCL was proposed.The chemical composition of the protective layers was studied using SEM-EDX,XRD,XPS,and Raman microspectroscopy.Anticorrosion protection level of the coated specimens was determined by means of electrochemical techniques,weight loss,and hydrogen evolution tests.The samples with hybrid layers showed the best corrosion protection during 23 h exposure to Hanks’Balanced Salt Solution(|Z|_(f=0.1 Hz)=1.02 MΩ·cm^(2),I_(C)=11 nA·cm^(-2),R_(p)=2.4 MΩ·cm^(2))and the lowest degradation rate(0.021 mm/year)after 7 day of exposure to HBSS among all the tested samples.The electrochemical activity on microscale of samples with the studied coatings was estimated by localized electrochemical techniques.The degradation mechanism of specimens with hybrid layers was proposed.The prospects of hybrid layer application in regulating the resorption process of Mg alloys were shown.展开更多
The bioactive constituents found in natural products(NPs)are crucial in protein-ligand interactions and drug discovery.However,it is difficult to identify ligand molecules from complex NPs that specifically bind to ta...The bioactive constituents found in natural products(NPs)are crucial in protein-ligand interactions and drug discovery.However,it is difficult to identify ligand molecules from complex NPs that specifically bind to target protein,which often requires time-consuming and labor-intensive processes such as isolation and enrichment.To address this issue,in this study we developed a method that combines ultra-high performance liquid chromatography-electrospray ionization-mass spectrometry(UHPLCESI-MS)with molecular dynamics(MD)simulation to identify and observe,rapidly and efficiently,the bioactive components in NPs that bind to specific protein target.In this method,a specific protein target was introduced online using a three-way valve to form a protein-ligand complex.The complex was then detected in real time using high-resolution MS to identify potential ligands.Based on our method,only 10 molecules from green tea(a representative natural product),including the commonly reported epigallocatechin gallate(EGCG)and epicatechin gallate(ECG),as well as the previously unreported eepicatechin(4β→8)-epigallocatechin 3-O-gallate(EC-EGCG)and eepiafzelechin 3-O-gallate-(4β→8)-epigallocatechin 3-O-gallate(EFG-EGCG),were screened out,which could form complexes with Aβ_(1-42)(a representative protein target),and could be potential ligands of Aβ_(1-42).Among of them,EC-EGCG demonstrated the highest binding free energy with Aβ_(1-42)(−68.54±3.82 kcal/mol).On the other side,even though the caffeine had the highest signal among green tea extracts,it was not observed to form a complex with Aβ_(1-42).Compared to other methods such as affinity selection mass spectrometry(ASMS)and native MS,our method is easy to operate and interpret the data.Undoubtedly,it provides a new methodology for potential drug discovery in NPs,and will accelerate the research on screening ligands for specific proteins from complex NPs.展开更多
Currently,endeavors to scale up the production of amorphous catalysts are still impeded by intricate synthesis conditions.Here,we have prepared a series of metal-based molybdate via one-step coprecipitation method.Aft...Currently,endeavors to scale up the production of amorphous catalysts are still impeded by intricate synthesis conditions.Here,we have prepared a series of metal-based molybdate via one-step coprecipitation method.After ingredient optimization,amorphous Co_(2)CeFe_(2)-MoO_(4) was identified as exhibiting the highest intrinsic activity among its counterparts.Modulation of electron structure enables Co_(2)CeFe_(2)-MoO_(4) to balance the adsorption behavior towards reactive intermediates.Ultimately,the obtained Co_(2)CeFe_(2)-MoO_(4) molybdate demonstrated a captivating OER performance,showcasing a low overpotential of 230 mV at 10 mA cm^(-2).Moreover,the alkaline electrolyzer employing the Co_(2)CeFe_(2)-MoO_(4) anode exhibited a low cell voltage of 1.50 V for water splitting and underwent an acceptable attenuation of 4.99% after 165 h of continuous operation,demonstrating its favorable catalytic activity and durability.This work provides a facile and eco-friendly synthesis pathway for crafting cost-effective and durable earth-abundant OER electrocatalysts tailored for water splitting to produce clean hydrogen.展开更多
文摘Just seeing off the BOth anniversary of the Institute of Chemistry, Chinese Academy of Sciences （ICCAS）, we are here with pleasure to conduct A Special Column for Young Scientists at ICCAS published in Chinese Chemistry Letters （CCL） endeavoring to disseminate positive energy of several enthusiastic chemists and spread their recent research to the global scientific community.
基金supported by the National Natural Science Foundation of China(Nos.92461313,12074387,and 92161114)the Innovation Capability Support Program of Shaanxi Province(No.2023-CX-TD-49).
文摘The structure and electronic properties of Co_(2)Ge_(10)^(-)anion and its neutral counterpart were investigated by anion photoelectron spectroscopy and theoretical calculations.The experimental vertical detachment energy of Co_(2)Ge_(10)^(-)was measured to be 2.86±0.08 eV.The lowest-energy isomer of Co_(2)Ge_(10)^(-)is in a doublet state and has a cage-like structure with Cs symmetry,which can be constructed by a tetragonal bipyramid on top of a pentagonal bipyramid and these two bipyramid structures share a common Co atom.The most stable structure of neutral Co_(2)Ge_(10)resembles its anionic counterpart and it is in a triplet state.The natural population analysis showed that the inner Co atom of both the anionic and neutral Co_(2)Ge_(10)acquires negative charge from the neighboring Ge atoms.The outer Co atom has a larger spin moment than the inner Co atom,indicating that the magnetic moments of Co_(2)Ge_(10)^(-/0)are mainly contributed by the outer Co atom.Analyses of the density of states and molecular orbitals indicated that there are a few highly delocalized molecular orbitals in Co_(2)Ge_(10)^(-),which are mainly contributed by Ge 4s atomic orbitals.
文摘Institute of Chemistry,Chinese Academy of Sciences(ICCAS)was established in 1956.ICCAS is a multidisciplinary research institute dedicated to the basic research in broad fields of chemical sciences,and to the key development of the innovative high-technology aiming at the imperative national needs and important strategic targets,as well as to the collaborative high-technology applications and transfers.With the development of 60 years,ICCAS has become one of the leading chemistry institutions in China with high international visibility.
基金financially supported by the National Natural Science Foundation of China(Nos.21873109 and 21922308)。
文摘Nucleation,which is the initial step of crystallization,critically governs the polymer crystallization behavior,influencing the crystallization temperature,kinetics,and morphology.However,the direct observation of the nucleation process in polymers remains elusive owing to spatial and temporal resolution limitations.This feature article summarizes the recent progress in understanding polymer nucleation within confined and interface-dominated environments,focusing on three representative systems:anodic aluminum oxide templates and nanocomposites containing nanoparticles or nanosheets.The interplay between finite size and interfacial effects has revealed some novel phenomena,such as homogeneous nucleation,surface nucleation,prefreezing,and supernucleation.
文摘It was in the 1980s that research on somatostatin(SST)in Alzheimer’s disease(AD)truly gained traction,demonstrating consistent colocalization with amyloid-β(Aβ),along with massive SST/SST cell losses(Almeida,2024).Although the field already had some grasp over the neuroendocrine and hypothalamic functions of the peptide,very little was known about the GABAergic interneurons(SST-INs)that synthesize it in cortical/hippocampal regions.Quite excitingly,over 40 years later,research has grown effervescent.
基金supported by a US-Senior Fulbright Award granted to Dr.A.Falodun for study at University of Mississippi,USA,CIESCs for the Fulbright awardthe University of Benin(Nigeria)and Institute of Chemistry(University of Rostock,Germany),for their support
文摘Picralima nitida Durand and Hook,(fam.Apocynaceae)is a West African plant with varied applications in African folk medicine.Various parts of the plant have been employed ethnomedicinally as remedy for fever,hypertension,jaundice,dysmenorrheal,gastrointestinal disorders and malaria.In order to reveal its full pharmacological and therapeutic potentials,die present review focuses on the current medicinal uses,phytochemistry,pharmacological and toxicological activities of this species.Literature survey on scientific journals,books as well as electronic sources have shown the isolation of alkaloids,tannins,polyphenols and steroids from different parts of the plant,pharmacological studies revealed that the extract or isolated compounds from this species posses analgesic,anti-inflammatory,hypoglyceamic,hypotensive,antiplasmodial,antimicrobial,antiulcer and antitumorigenic activities.Results from various scientific investigations to date have revealed the potential of the extract from the plant or isolated compounds for use in the treatment and prevention of various kinds of human diseases.However,further studies on the extracts and pure compounds from this species is required to completely assess its phytoc-hemical,pharmacological and toxicological profile as well as the mechanism of action behind these pharmacological activities exhibited by the compounds isolated from this species.
文摘The electrochemistry of polyaniline synthesized electrochemically in acidic solution under light irradiation has been studied as a function of the applied potentials, the concentration and acidity of electrolyte as well as pH at applied potentials in the rang+0.40 to-0.5V vs. SCE. It is concluded that under selected experimental conditions the reduced repeat groups in polyaniline are oxidized by air in the dark and that this oxidation process can be strongly photocatalyzed.
基金the National Basic Research Program of China(973 Program,No.2014CB643502)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB12010200)the National Natural Science Foundation of China(No.91333113)for financial support
文摘Organic photovoltaics and field-effect transistors have attracted considerable attention due to the easy fabrication,low cost,light weight,and flexibility.Unsymmetrical conjugated building blocks are widely utilized for the design of new organic π-functional materials in order to achieve high-performance electronic devices,which has become a hot research topic in recent years.In this review,we summarized some typical organic π-functional materials with regioregular conjugated backbones with unsymmetrical electron-deficiency moieties and focused on the influence of regiochemistry on the final device performance.
文摘Diphenylchlorin (DPC) and diphenylbacteriochlorin (DPBC) were synthesized for the first time from reduction of 5,10-diphenylporphyrin (DPP). As photosensitizers they have sizable absorption in the red region of the visible spectrum. The high yield of DPC.-photosensitized generation Of O-1(2), and the EPR studies in homogenerous solution showed that the photodynamic action of DPP-based photosensitizers may proceed via type I and type II machanisms.
基金supported by National Natural Science Founda-tion of China(22179070,22109083,22108151,22075029,and 22061132002)China Postdoctoral Science Foundation(BX2021135,2021TQ0164)+1 种基金the Seed Fund of Shanxi Research In-stitute for Clean Energy(SXKYJF015)the Tsinghua University Initiative Scientific Research Program,and the“Shuimu Tsinghua Scholar Program of Tsinghua University”.
文摘Dendrite growth of lithium(Li)metal anode severely hinders its practical application,while the situation becomes more serious at low temperatures due to the sluggish kinetics of Liion diffusion.This perspective is intended to clearly understand the energy chemistry of lowtemperature Li metal batteries(LMBs).The lowtemperature chemistries between LMBs and traditional Liion batteries are firstly compared to figure out the features of the lowtemperature LMBs.Li deposition behaviors at low temperatures are then discussed concerning the variation in Liion diffusion behaviors and solid electrolyte interphase(SEI)features.Subsequently,the strategies to enhance the diffusion kinetics of Li ions and suppress dendrite growth including designing electrolytes and electrode/electrolyte interfaces are analyzed.Finally,conclusions and outlooks are drawn to shed lights on the future design of highperformance lowtemperature LMBs.
基金This research was financially supported by the Key Laboratory Foundation of Polymer Materials of Gansu Province
文摘The multi-bond dissociation dynamics of oxalyl bromide （（BrCO）2） has been investigated by DFT and CIS calculations. Upon the results, conclusion could be drawn that dissociation of C-Br bond of oxalyl bromide at the ground state （So） is of barfierless. After the absorption of a photon, （BrCO）2 is excited to the first excited state and one of its C-Br bonds is broken to yield Br ·＊ and BrCOCO· ＊ free radicals. In addition, BrCOCO · ＊ with high energy is apt to release energy, and ultimately, turns into BrCOCO ·of the ground state. The energy is adequate for BrCOCO· to break down into Br · and 2CO; at the same time the C-C and C-Br bonds of BrCOCO · free radicals dissociate.
基金supported by the Major State Basic Research Development Program(Grant No.F2000078100)the National Natural Science Foundation of China(No.20172059)the Found of Chinese Academy of Sciences.
文摘A solid-phase synthesis of 1α-hydroxylation of 5,6-trans-vitamin D3 8 is described.The solid phase resin acts as a special protecting group, which gives a higher stereoselectivity in oxidation step than classical protecting groups. The stereochemistry control is favored by using high crosslinkage polymer support in a poor solvent. This work may be of benefit to the synthesis of vitamin D system.
基金Financial supports from the IR INFRANALYTICS FR2054from Slovak grant agency (VEGA 2/0046/22)+1 种基金ITMS project (with code 313021T081) supported by Research and Innovation Operational program funded by the ERDFthe Kazan Federal University Strategic Academic Leadership Program》 (Priority-2030)。
文摘For the first time,the mechanism of metal aluminum dissolution in NaF-ScF_(3) eutectic melts and the chemical interaction between the constituents of this mixture have been thoroughly studied by a combination of differential thermal analysis(DTA),high temperature and solid-state nuclear magnetic resonance(NMR),and X-ray diffraction(XRD) coupled with the molecular dynamic simulations.The formation of an insoluble Al_(3)Sc alloy in molten(NaF-ScF_(3))_(eut)system was proven,and the chemical mechanism of this aluminothermic Al_(3)Sc alloy production was elucidated.Corresponding ex situ examinations bring to light the formation of NaScF_4 and solid solution of Na_(3)(Al,Sc)F_(6) in cooled bath.The molecular dynamics calculations of the bath allow us to construct the structural model and to predict viscosity,density and electrical conductivity of the reagent melt to help to optimize the conditions of the alloy synthesis.
文摘A new method of synthesis of 2-(1,2-diferrocenylvinyl)benz- and azabenzimidazoles (3a-f), (4a-f) and 1’H,3’H(Me)-spiro-[(aza)benzimidazoline-2’,3-(1,2-diferrocenylcyclopropenes)] (5a-f) via reactions of diferrocenyl(methylsulfanyl)cyclopropenylium iodide (1) with aromatic o-diamines (2a-f) in the presence of Et3N (80°C - 82°C) is described. The structures of the resultant compounds are established using IR, 1H and 13C NMR spectroscopy, mass spectrometry and elemental analysis. The structure of one compound, cis-2-(1,2-diferrocenylvinyl)-1-methylbenzimidazole (3b), is confirmed by X-ray diffraction analysis. The electrochemical properties of compounds 3a, 3b, 3d and 5f are investigated using cyclic square wave voltammetry. Two electrochemical processes (I-II), attributed to oxidation of the ferrocene moieties, and the values of E0’(I), E0’(II), DE0’(II-I) and comporportionation constant Kcom are reported. The bioactivities of seven compounds 3a, 3c-f, 5d, 5f are evaluated. Compound 5f is the most active compound with a modest cytotoxic activity against six human cancer cell lines: U-251 (glioma), PC-3 (prostate cancer), K-562 (leukemia), HCT-15 (colon cancer), MCF-7 (breast cancer) and SKLU-1 (lung cancer).
文摘As one of the fundamental and key disciplines of natural sciences, chemistry deals with the properties, composition, structure, transformation and applications of substances.It could be further divided into several branches, such as inorganic chemistry, organic chemistry, physical chemistry, polymer chemistry, analytical chemistry and chemical engineering.In recent years, many new branches and fields have emerged amide the continuous development of chemistry and its interdisciplinary research with mathematics, physics, astronomy, earth science, biology, medical science, materials science, and environmental science.
基金supported by the National Natural Science Foundation of China(52303257,52321006,T2394480,and T2394484)the National Key R&D Program of China(Grant No.2023YFE0111500)+3 种基金Key Research&Development and Promotion of Special Project(Scientific Problem Tackling)of Henan Province(242102211090)the China Postdoctoral Science Foundation(2023TQ0300,and 2023M743171)the Postdoctoral Fellowship Program(Grade B)of China Postdoctoral Science Foundation(GZB20230666)College Student Innovation and Entrepreneurship Training Program of Zhengzhou University(202410459200)。
文摘Flexible wearable optoelectronic devices fabricated fromorganic–inorganic hybrid perovskites significantly accelerate the developmentof portable energy,biomedicine,and sensing fields,but their poor thermal stabilityhinders further applications.Conversely,all-inorganic perovskites possessexcellent thermal stability,but black-phase all-inorganic perovskite filmusually requires high-temperature annealing steps,which increases energy consumptionand is not conducive to the fabrication of flexible wearable devices.In this work,an unprecedented low-temperature fabrication of stable blackphaseCsPbI3perovskite films is demonstrated by the in situ hydrolysis reactionof diphenylphosphinic chloride additive.The released diphenyl phosphateand chloride ions during the hydrolysis reaction significantly lower the phasetransition temperature and effectively passivate the defects in the perovskitefilms,yielding high-performance photodetectors with a responsivity of 42.1 AW−1 and a detectivity of 1.3×10^(14)Jones.Furthermore,high-fidelity imageand photoplethysmography sensors are demonstrated based on the fabricated flexible wearable photodetectors.This work provides a newperspective for the low-temperature fabrication of large-area all-inorganic perovskite flexible optoelectronic devices.
基金financially supported by the National Natural Science Foundation of China (Nos. 52173013 and 52373015)。
文摘Polybutene-1(PB-1) is a semi-crystalline polymer with excellent mechanical properties. However, its practical application is significantly hindered by the slow Form Ⅱ-Ⅰ transition, which can take up to several days to complete. While prior research established that long-chain branching(LCB) structures synthesized via ω-alkenylmethyldichlorosilane copolymerization-hydrolysis(ACH) chemistry markedly accelerate this transition, this work demonstrates that H-shaped LCB structures constructed through copolymerization with 1,9-decadiene exhibit the capability to facilitate Form Ⅱ-Ⅰ transition in most systems evaluated herein. However, low branching efficiency concurrently generates extended alkyl pendant chains, which impose pronounced steric-hindrance-driven suppression on the transition kinetics, thereby substantially diminishing the net acceleration effect of the LCB structures, even resulting in a net retardation effect in certain systems. Notably, a significant synergistic acceleration effect emerged between the H-shaped LCB structures and propylene comonomer units. These findings confirm that the H-shaped LCB structures play a role in promoting the Form II-I transformation process, which is independent of the synthetic pathways, thereby providing more strategies for addressing the long-standing processing problems of PB-1.
基金supported by Russian Science Foundation,Russia(project no.24-73-10008,https://rscf.ru/en/project/24-73-10008/)the government assignments from the Ministry of Science and Higher Education of the RF,Russia(project no.FWFN-2024-0001).
文摘This article discusses potential solutions to overcome current limitations for clinical implementation of Mg implants by forming the biocompatible hybrid PEO-based inhibitor-and polymer-containing coatings for a controlled corrosion degradation of the bioresorbable material.Multifunctional hybrid coatings were obtained on MA8 magnesium alloy.The porous ceramic-like coating synthesized by plasma electrolytic oxidation served as a base for further modification with bioresorbable polymer(polycaprolactone,PCL)contained halloysite nanotubes(HNTs)with corrosion inhibitor(benzotriazole,BTA).The method for HNT impregnating with BTA and introducing them into the matrix of PCL was proposed.The chemical composition of the protective layers was studied using SEM-EDX,XRD,XPS,and Raman microspectroscopy.Anticorrosion protection level of the coated specimens was determined by means of electrochemical techniques,weight loss,and hydrogen evolution tests.The samples with hybrid layers showed the best corrosion protection during 23 h exposure to Hanks’Balanced Salt Solution(|Z|_(f=0.1 Hz)=1.02 MΩ·cm^(2),I_(C)=11 nA·cm^(-2),R_(p)=2.4 MΩ·cm^(2))and the lowest degradation rate(0.021 mm/year)after 7 day of exposure to HBSS among all the tested samples.The electrochemical activity on microscale of samples with the studied coatings was estimated by localized electrochemical techniques.The degradation mechanism of specimens with hybrid layers was proposed.The prospects of hybrid layer application in regulating the resorption process of Mg alloys were shown.
基金supported by the National Key R&D Program of China(No.2018YFA0800900).
文摘The bioactive constituents found in natural products(NPs)are crucial in protein-ligand interactions and drug discovery.However,it is difficult to identify ligand molecules from complex NPs that specifically bind to target protein,which often requires time-consuming and labor-intensive processes such as isolation and enrichment.To address this issue,in this study we developed a method that combines ultra-high performance liquid chromatography-electrospray ionization-mass spectrometry(UHPLCESI-MS)with molecular dynamics(MD)simulation to identify and observe,rapidly and efficiently,the bioactive components in NPs that bind to specific protein target.In this method,a specific protein target was introduced online using a three-way valve to form a protein-ligand complex.The complex was then detected in real time using high-resolution MS to identify potential ligands.Based on our method,only 10 molecules from green tea(a representative natural product),including the commonly reported epigallocatechin gallate(EGCG)and epicatechin gallate(ECG),as well as the previously unreported eepicatechin(4β→8)-epigallocatechin 3-O-gallate(EC-EGCG)and eepiafzelechin 3-O-gallate-(4β→8)-epigallocatechin 3-O-gallate(EFG-EGCG),were screened out,which could form complexes with Aβ_(1-42)(a representative protein target),and could be potential ligands of Aβ_(1-42).Among of them,EC-EGCG demonstrated the highest binding free energy with Aβ_(1-42)(−68.54±3.82 kcal/mol).On the other side,even though the caffeine had the highest signal among green tea extracts,it was not observed to form a complex with Aβ_(1-42).Compared to other methods such as affinity selection mass spectrometry(ASMS)and native MS,our method is easy to operate and interpret the data.Undoubtedly,it provides a new methodology for potential drug discovery in NPs,and will accelerate the research on screening ligands for specific proteins from complex NPs.
基金supported by the National Natural Science Foundation of China (No. 21872153)。
文摘Currently,endeavors to scale up the production of amorphous catalysts are still impeded by intricate synthesis conditions.Here,we have prepared a series of metal-based molybdate via one-step coprecipitation method.After ingredient optimization,amorphous Co_(2)CeFe_(2)-MoO_(4) was identified as exhibiting the highest intrinsic activity among its counterparts.Modulation of electron structure enables Co_(2)CeFe_(2)-MoO_(4) to balance the adsorption behavior towards reactive intermediates.Ultimately,the obtained Co_(2)CeFe_(2)-MoO_(4) molybdate demonstrated a captivating OER performance,showcasing a low overpotential of 230 mV at 10 mA cm^(-2).Moreover,the alkaline electrolyzer employing the Co_(2)CeFe_(2)-MoO_(4) anode exhibited a low cell voltage of 1.50 V for water splitting and underwent an acceptable attenuation of 4.99% after 165 h of continuous operation,demonstrating its favorable catalytic activity and durability.This work provides a facile and eco-friendly synthesis pathway for crafting cost-effective and durable earth-abundant OER electrocatalysts tailored for water splitting to produce clean hydrogen.
